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US12104045B2 - Opaque multi-layer body made of polycarbonate and having weathering stability - Google Patents

Opaque multi-layer body made of polycarbonate and having weathering stability Download PDF

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Publication number
US12104045B2
US12104045B2 US15/733,860 US201915733860A US12104045B2 US 12104045 B2 US12104045 B2 US 12104045B2 US 201915733860 A US201915733860 A US 201915733860A US 12104045 B2 US12104045 B2 US 12104045B2
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Prior art keywords
titanium dioxide
coating
weight
colorants
substrate layer
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US20210221977A1 (en
Inventor
Alexander Meyer
Joerg Reichenauer
Ulrich Blaschke
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Covestro Deutschland AG
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Covestro Intellectual Property GmbH and Co KG
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Definitions

  • the present invention relates to an opaque multilayer article comprising a thermoplastic layer based on polymethylmethacrylate or aromatic polycarbonate, comprising titanium dioxide, optionally a primer layer and a topcoat layer.
  • the multilayer article of the invention is notable for high color stability and weathering stability.
  • Thermoplastic polymers for example polycarbonate
  • polycarbonate offer many advantages over conventional materials for use in the vehicle sector and for buildings etc. These include, for example, elevated fracture resistance and/or a weight saving, which in the case of outer automobile parts allow greater safety and lower fuel consumption. They also enable a high level of design freedom.
  • thermoplastics for example, compositions based on aromatic polycarbonate and/or polymethylmethacrylate (PMMA) are of particularly good suitability for use as outer material. Owing to high toughness, aromatic polycarbonate in particular has a very good profile of properties for such end uses.
  • PMMA polymethylmethacrylate
  • titanium dioxide has high photoactivity and hence can itself contribute to the breakdown of colorants and also of the thermoplastic matrix, or is a major cause of breakdown.
  • titanium dioxide itself can attack the thermoplastic matrix even in the absence of light or UV irradiation.
  • thermoplastic materials especially in the case of polycarbonate
  • titanium dioxide grades have been developed for thermoplastic matrices. These titanium dioxide grades have an optimized coating or shell or sequence of shells, which enable compatibility with the respective polymer matrix and also reduce photoactivity. Such optimized titanium dioxide grades are described, for example, in DE 102008058351 A1. Commercially available titanium dioxide grades optimized for polycarbonate are, for example, Kronos 2230 and Kronos 2233 (Kronos Worldwide Inc.). However, it has been found that these grades too, in combination with colorants, lead to significant color shifts after weathering, and there is a need for improvement here.
  • titanium dioxide as white pigment in thermoplastic materials is necessary in order to assure the high color brilliance required for outside applications in opaque colors. Attempts to replace titanium dioxide with other white pigments such as barium sulfate, kaolin, zinc sulfide etc., showed that it is not possible in this way to improve color stability or achieve the necessary color brilliance. For all opaque colors—except in the field of black colors—the use of titanium dioxide is thus absolutely necessary.
  • thermoplastic materials can be stabilized by the use of particular additives. For instance, weathering stability can be improved by use of UV absorbers. However, this can achieve only inadequate color stabilization.
  • stabilizer combinations of UV absorbers and free-radical scavengers These especially include combinations of UV absorbers and HALS (hindered amine light stabilizers). Combinations of this kind are employable for particular thermoplastic matrices such as polyolefins and are described, for example, by Rajan et al. in J. of Appl. Pol. Sci. 2012, Vol. 124, 4007-4015, Moura et al. in Dyes and Pigments 1997, Vol. 33, No.
  • coating of polycarbonate can increase weathering stability. Coatings of this kind are described, for example, in U.S. Pat. No. 5,041,313 A, DE 3121385 A1, U.S. Pat. No. 5,391,795 A, WO 2008/109072 A1. However, it has been shown that such coatings can merely delay color shifts and chalking effects in the case of opaque colors. Even with such coatings, in the case of non-black opaque colors, there are significant changes within relatively short weathering times, such as loss of gloss, color shift or bleaching effects.
  • Color brilliance is a subjective impression that the eye or human brain perceives from the color. This impression correlates with high color saturation and also the spectral composition of the color. It is also important that gloss is good. As well as hue and brightness, color brilliance is one of the properties of a color that is perceived as being significant by man.
  • the proportions of the elements in atom % in the coating have preferably been determined by means of x-ray photo electron spectroscopy. It will be apparent that, according to the thickness of the coating, the detection angle should be chosen appropriately such that the entire coating layer is covered.
  • the preparation and sample handling are preferably in accordance with ISO 18117:2009-06 and ISO 18116:2005-08.
  • multilayer article in the context of the invention is “at least two layers”, namely a substrate layer and a topcoat layer intended to lie on the side of the multilayer article oriented “to the outside” in the use state, i.e. toward the light source, i.e. toward the sun.
  • a primer layer between topcoat layer and substrate layer.
  • protective and functional layers especially a second topcoat layer and optionally primer layer, on the opposite side of the substrate layer.
  • the multilayer articles of the invention are colored.
  • the specified properties of the titanium dioxide relate to any titanium dioxide present in the composition. This may be titanium dioxide from one batch or titanium dioxide from various batches or even various products. In these cases, the averages are formed for the respective properties. It will thus be apparent that, for example, as well as Altiris® 800 from Huntsman used in the examples, for example, Kronos 2230 may also be present, provided that the profile of properties composed of the average values corresponds to that according to the claims.
  • the titanium dioxide has a median particle size D50, determined by means of scanning electron microscopy (STEM), of ⁇ 0.3 ⁇ m, preferably >0.40 ⁇ m, further preferably >0.5 ⁇ m, especially preferably >0.55 ⁇ m, especially preferably 0.6 to 1.2 ⁇ m, exceptionally preferably 0.65 to 1.15 ⁇ m.
  • STEM scanning electron microscopy
  • the titanium dioxide present in the composition of the substrate layer is a titanium dioxide of the rutile type to an extent of at least 60% by weight, preferably to an extent of at least 70% by weight, further preferably to an extent of at least 80% by weight, even further preferably to an extent of at least 90% by weight, especially preferably to an extent of at least 95% by weight, very especially preferably to an extent of at least 99% by weight, based in each case on the overall crystal structures of the titanium dioxide.
  • the titanium dioxide is of the rutile type to an extent of 100% by weight.
  • the titanium dioxide present in the composition of the substrate layer has a coating containing silicon dioxide and aluminum oxide and optionally titanium dioxide, where the ratio of the sum total of the aluminum content and silicon content in atom % in the coating to the titanium content in atom % in the coating is greater than 5:1, preferably greater than 10:1, further preferably at least 15:1, even further preferably at least 20:1.
  • the ratio of the sum total of the aluminum content and silicon content in atom % in the coating to the titanium content in atom % in the coating at a detection angle of 10° is at least 15:1, at a detection angle of 45° is at least 19:1, further preferably at least 20:1, and at a detection angle of 80° is likewise preferably at least 20:1.
  • the coating itself may also be free of any titanium dioxide.
  • the coating may be a mixed layer comprising the abovementioned oxides, or a sequence of the different oxide layers.
  • the coating has a silicon dioxide layer and an aluminum oxide layer, further preferably with the silicon dioxide layer between the titanium dioxide core and the aluminum oxide layer.
  • the titanium dioxide does not have any inorganic layers other than the titanium dioxide core, the silicon dioxide layer and the aluminum oxide layer, but these may be contaminated by elements such as carbon, titanium, sodium, potassium etc.
  • the titanium dioxide may also contain an organic layer as well as inorganic layers. This may comprise polysiloxanes and/or polyols.
  • the coating is included in the total amount of the titanium dioxide in the thermoplastic composition, such that the actual proportion of titanium dioxide in the titanium dioxide component in the composition is smaller. If the composition contains, for example, 1.5% by weight of titanium dioxide, the composition does in fact contain less than 1.5% by weight of pure titanium dioxide since the coating containing aluminum oxide and silicon dioxide is also counted in the stated amount.
  • the proportion of pure titanium dioxide in the titanium dioxide component is at least 90% by weight, preferably at least 92% by weight, more preferably more than 93% by weight, determined to ASTM D 1394:2014.
  • the titanium dioxide used for the composition of the substrate layer is exclusively that which has the features mentioned in the four paragraphs above.
  • the proportion of titanium dioxide including its coating in the thermoplastic composition of the substrate layer is preferably 0.05% to 2.5% by weight, further preferably 0.1% to 2.0% by weight, even further preferably 0.10% to 1.5% by weight.
  • the titanium dioxide used in accordance with the invention is a white pigment, Ti(IV)O 2 .
  • Colored titanium dioxides contain, as well as titanium, also elements such as Sb, Ni, Cr in significant amounts, so as to result in a color impression other than “white”. It will be apparent that traces of other elements may also be present as impurities in the titanium dioxide white pigment. However, these amounts are so small that the titanium dioxide does not take on any hue as a result.
  • the coating layer preferably has a thickness of 5 to 20 ⁇ m, more preferably 8 to 17 nm, most preferably 10 to 15 nm.
  • compositions of the substrate layer contain at least one organic colorant. This is preferably selected from the group consisting of those based on anthraquinone, perinone, pyrazolone, indanthrone, methine, phthalocyanine structures, and on azo or diazo dyes.
  • organic colorants are those selected from the structures (1) to (18) shown below, where preferably at least one organic colorant of these structures is present in the opaque thermoplastic polymer compositions of the invention for the substrate layer.
  • further colorants selected from the same group of colorants and/or generally from the group of colorants to be present.
  • organic green colorants are colorants of the formulae (1) and (2a/2b/2c):
  • the colorant of the formula (1) is known by the name Macrolex Green 5B from Lanxess Deutschland GmbH. Color Index number 61565. CAS number: 128-90-3, and is an anthraquinone dye.
  • Colorants of the formulae (2a), (2b) and (2c) are known by the name Macrolex Green G (Solvent Green 28).
  • Blue colorants that are used are preferably colorants of the formulae (3) and/or (4a/4b):
  • Rc and/or Rd are Cl and are in o and/or p positions to the carbon atoms bearing the amine functionalities, for example di-orthochloronaphthaleno, di-ortho, mono-para-chloronaphthaleno and mono-ortho-naphthaleno.
  • Rc and Rd are each a tert-butyl radical which is preferably in the meta position to the carbon atoms bearing the nitrogen functionalities.
  • blue colorants include:
  • the red colorant used is preferably a colorant of the formula (7), available under the “Macrolex Red 5B” name, with CAS number 81-39-0:
  • Violet colorants used with preference are colorants of the formulae (10) with CAS number 61951-89-1, (11), available under the “Macrolex Violet B” name from Lanxess AG, with CAS number 81-48-1 or (12a/12b):
  • Ra and/or Rb are Cl and are in o and/or p positions to the carbon atoms bearing the amine functionalities, for example di-orthochloronaphthaleno, di-ortho, mono-para-chloronaphthaleno and mono-ortho-naphthaleno.
  • Ra and Rb are each a tert-butyl radical which is preferably in the meta position to the carbon atoms bearing the nitrogen functionalities.
  • thermoplastic composition of the substrate layer aside from the titanium dioxide pigment, contains only one or more colorants from the group of colorants of the formulae (1) to (18), Amaplast Yellow GHS, the Heliogen Blue grades and/or the Heliogen Green grades, but no further colorants, especially also no other pigments and no carbon black.
  • the organic colorants disclosed in the context of the present invention are preferably used, based on the respective individual component, in amounts of 0.0010% to 1.00% by weight, preferably of 0.005% by weight to 0.80% by weight and more preferably of 0.01% by weight to 0.70% by weight in thermoplastic polymer compositions.
  • the total concentration of organic and inorganic colorants, including pigments, except for TiO 2 is further preferably 0.012% to 1.2% by weight, especially preferably 0.012% to 1.0% by weight, based on a resulting polymer composition containing the organic colorants of the invention or organic colorant combinations.
  • compositions preferably contain ⁇ 0.001% by weight, preferably ⁇ 0.01% by weight, of organic colorants.
  • Inorganic colorants that are suitable in principle are, for example, mixed phase oxide pigments such as iron oxides, titanates such as Cr, Sb, Zn and Ni titanates, spinel pigments, silicate-based pigments such as aluminosilicates, e.g. ultramarine.
  • mixed phase oxide pigments such as iron oxides, titanates such as Cr, Sb, Zn and Ni titanates
  • spinel pigments such as spinel pigments
  • silicate-based pigments such as aluminosilicates, e.g. ultramarine.
  • the substrate layer may, as well as the aromatic polycarbonate or the polymethylmethacrylate on which it is based, also contain, as blend partner, one or more further thermoplastics, preferably aromatic polycarbonate including copolycarbonate, polyestercarbonate, polystyrene, styrene copolymers, aromatic polyesters such as polyethylene terephthalate (PET), PET-cyclohexanedimethanol copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), cyclic polyolefin, polyacrylate, copolyacrylate, polymethacrylate, copolymethacrylate, for example poly- or copolymethylmethacrylate (such as PMMA), copolymers with styrene, for example transparent polystyrene-acrylonitrile (PSAN), thermoplastic polyurethanes, polymers based on cyclic olefins (e.g.
  • TOPAS® a product commercially available from Ticona
  • the thermoplastic together with all the other components of the substrate layer forms 100% by weight.
  • 0% to a maximum of 5.0% by weight of blend partners is present, more preferably no blend partners at all.
  • Polycarbonate including copolycarbonate, and PMMA are useful as blend partners when the base polymer of the thermoplastic composition is the respective other polymer.
  • Suitable polycarbonates for the production of the plastics composition of the invention are any of the known polycarbonates. These are homopolycarbonates and copolycarbonates. Where reference is made to “polycarbonates” in the context of the present invention, what are meant are preferably aromatic polycarbonates. More preferably, polyestercarbonates are excluded from the polycarbonates in the context of the invention.
  • the suitable polycarbonates preferably have average molecular weights M w of 10 000 g/mol to 40 000 g/mol, preferably of 14 000 g/mol to 35 000 g/mol and more preferably of 16 000 g/mol to 32 000 g/mol.
  • the M w values here are determined by gel permeation chromatography using dichloromethane as eluent, calibration with linear polycarbonates (formed from bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany; calibration by method 2301-0257502-09D (from 2009, in German) from Currenta GmbH & Co. OHG, Leverkusen.
  • the eluent for the calibration is likewise dichloromethane.
  • the melt volume flow rate (MVR), determined to ISO 1133-1:2012-03 at 300° C. with load 1.2 kg, is 7 to 40 cm 3 /(10 min), preferably 8 to 35 cm 3 /(10 min).
  • the polycarbonates are preferably prepared by the interfacial process or the melt transesterification process, which have been described many times in the literature.
  • melt transesterification process is described, for example, in the “Encyclopedia of Polymer Science”, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964), and in patent specifications DE 10 31 512 A and U.S. Pat. No. 6,228,973 B1.
  • the polycarbonates are preferably prepared by reactions of bisphenol compounds with carbonic acid compounds, especially phosgene, or of diphenyl carbonate or dimethyl carbonate in the melt transesterification process.
  • the polycarbonates may be linear or branched. It is also possible to use mixtures of branched and unbranched polycarbonates.
  • Suitable branching agents for the preparation of branched polycarbonates are known from the literature and described, for example, in the patent documents U.S. Pat. No. 4,185,009 B and DE 25 00 092 A1 (3,3-bis(4-hydroxyaryloxindoles), see whole document in each case), DE 42 40 313 A1 (see page 3, lines 33 to 55), DE 19 943 642 A1 (see page 5, lines 25 to 34) and U.S. Pat. No. 5,367,044 B and literature cited therein.
  • the polycarbonates used may additionally also be intrinsically branched, in which case no branching agent is added in the course of polycarbonate preparation.
  • intrinsic branches is that of so-called Fries structures, as described for melt polycarbonates in EP 1 506 249 A1.
  • chain terminators may be used in polycarbonate preparation.
  • Chain terminators used are preferably phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol or cumylphenol or a mixture thereof.
  • thermoplastic polymer compositions may, as well as the colorants of the invention and titanium dioxide, optionally also contain one or more further components.
  • these include: UV absorbers (component iii). If present, these are preferably present in amounts of 0.10% by weight to 1.00% by weight, further preferably to 0.6% by weight, even further preferably 0.10% by weight to 0.50% by weight, and most preferably 0.10% by weight to 0.30% by weight.
  • Suitable UV absorbers are described, for example, in EP 1 308 084 A1, in DE 102007011069 A1 and in DE 10311063 A1.
  • UV absorbers include the following: hydroxybenzotriazoles, such as 2-(3′,5′-bis(1,1-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole (Tinuvin® 234, BASF SE, Ludwigshafen), 2-(2′-hydroxy-5′-(tert-octyl)phenyl)benzotriazole (Tinuvin® 329, BASF SE, Ludwigshafen), 2-(2′-hydroxy-3′-(2-butyl)-5′-(tert-butyl)phenyl)benzotriazole (Tinuvin® 350, BASF SE, Ludwigshafen), bis(3-(2H-benzotriazolyl)-2-hydroxy-5-tert-octyl)methane, (Tinuvin® 360, BASF SE, Ludwigshafen), (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol (Tinuvin® 1577
  • the polymer composition of the substrate layer contains at least one UV absorber as component iii).
  • the mixture contains 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol (Tinuvin 326) or 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenol)-1,3,5-triazine, known by the ADK STAB LA-F70 trade name from Adeka Palmerole.
  • the polymer composition preferably contains at least one thermal stabilizer as component iv).
  • the amount of thermal stabilizer is preferably up to 0.20% by weight, further preferably 0.01% to 0.10% by weight, even further preferably 0.01% to 0.05% by weight, especially preferably 0.015% to 0.040% by weight, based on the overall composition.
  • Preferred thermal stabilizers are phosphites and phosphonites, and also phosphines. Examples include triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl
  • triphenylphosphine TPP
  • Irgafos® 168 tris(2,4-di-tert-butylphenyl) phosphite) or tris(nonylphenyl) phosphite or mixtures thereof are used.
  • alkyl phosphates for example mono-, di- and/or trihexyl phosphate, triisooctyl phosphate and/or trinonyl phosphate.
  • the alkyl phosphate used is preferably triisooctyl phosphate (tris-2-ethylhexyl phosphate). It is also possible to use mixtures of various mono-, di- and trialkyl phosphates.
  • alkyl phosphates are used, these are preferably used in an amount of less than 0.05% by weight, further preferably of 0.00005% to 0.05% by weight, even further preferably of 0.0002% to 0.05% by weight, especially preferably of 0.0005% to 0.03% by weight, very especially preferably of 0.001% to 0.0120% by weight, based on the overall composition.
  • phenolic antioxidants such as alkylated monophenols, alkylated thioalkylphenols, hydroquinones and alkylated hydroquinones.
  • Irganox® 1010 penentaerythritol 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate; CAS: 6683-19-8) and Irganox 1076® (2,6-di-tert-butyl-4-(octadecanoxycarbonylethyl)phenol).
  • the composition preferably contains, as component v, demolding agents, further preferably based on a fatty acid ester, even further preferably based on a stearic ester, especially preferably based on pentaerythritol. Particular preference is given to using pentaerythritol tetrastearate (PETS) and/or glycerol monostearate (GMS). If one or more demolding agents are used, the amount is preferably up to 1.0% by weight (inclusive), further preferably 0.01% to 0.50% by weight, especially preferably 0.01% to 0.40% by weight, based in each case on the overall composition.
  • demolding agents further preferably based on a fatty acid ester, even further preferably based on a stearic ester, especially preferably based on pentaerythritol. Particular preference is given to using pentaerythritol tetrastearate (PETS) and/or glycerol monoste
  • component vi additives, optionally in addition to the one or more UV absorbers and/or thermal stabilizers and/or demolding agents according to components iii to v, preferably 0.0% by weight to 10.0% by weight, further preferably to 5.0% by weight, even further preferably 0.01% by weight of 3.00% by weight, more preferably 0.01% to 1.00% by weight, of further additives.
  • Components iii to v are explicitly excluded from this component vi. The same applies to components i (titanium dioxide) and ii (organic colorant).
  • the polymer composition in any case contains two colorants, of which neither of the at least two colorants is carbon black.
  • the polymer composition may, however, optionally contain carbon black as a further additive.
  • the carbon black in this case is preferably finely dispersed in the organic polymer matrix and is preferably in nanoscale form.
  • Suitable carbon blacks have an average particle size of preferably less than 100 nm, further preferably less than 75 nm, even further preferably less than 50 nm and more preferably less than 40 nm, the average particle size preferably being greater than 0.5 nm, further preferably greater than 1 nm and more preferably greater than 5 nm.
  • the particle size is determined by TEM (transmission electron microscopy).
  • compositions of the invention preferably contain less than 0.01% by weight, further preferably ⁇ 0.005% by weight, even further preferably ⁇ 0.001% by weight, of carbon black; they are more preferably free of carbon black.
  • polymer compositions of the invention comprising the abovementioned components are produced by standard methods of incorporation by combining, mixing and homogenizing, with the homogenization in particular preferably taking place in the melt with application of shear forces. Combination and mixing is optionally effected prior to melt homogenization using powder premixtures.
  • premixtures which have been produced from solutions of the mixture components in suitable solvents, wherein homogenization is optionally effected in solution and the solvent is then removed. It is especially possible here to introduce the components of the composition of the invention by known methods, including as a masterbatch.
  • the use of masterbatches and of powder mixtures or compacted premixtures is especially suitable for introduction of the abovementioned additives. It is optionally possible here to premix all the aforementioned components. Alternatively, however, premixtures and masterbatches of colorants and any other combinations are also possible. In all cases, for better meterability in the production of the thermoplastic polymer compositions, the aforementioned component premixtures are preferably made up with pulverulent polymer component, aromatic polycarbonate or PMMA according to the main component of the thermoplastic composition, in such a way as to result in easily handled overall volumes.
  • the abovementioned components may be mixed to give a masterbatch, in which case the mixing preferably takes place in the melt under the action of shear forces (for example in a kneader or twin-screw extruder).
  • shear forces for example in a kneader or twin-screw extruder.
  • the polymer matrix chosen is preferably the thermoplastic that also constitutes the main component of the ultimate overall polymer composition.
  • the composition can be combined, mixed, homogenized and then extruded in standard apparatuses such as screw extruders (for example twin-screw extruders (TSE)), kneaders or Brabender or Banbury mills. After extrusion, the extrudate may be chilled and comminuted.
  • screw extruders for example twin-screw extruders (TSE)
  • kneaders for example twin-screw extruders (TSE)
  • kneaders for example twin-screw extruders (TSE)
  • kneaders kneaders
  • Brabender Brabender
  • Banbury mills kneaders
  • the extrudate may be chilled and comminuted.
  • the multilayer article comprises not only the substrate layer but also one or more topcoat layers c.
  • these layers preferably fulfil the function of scratch resistance layers and/or weathering protection layers.
  • the topcoat layers have been applied either on one or both sides.
  • they cover part of the surface of the substrate layer or else the entire substrate layer.
  • at least part of the surface of the substrate layer has a corresponding coating, relating to the surface visible to the outside in the desired application.
  • the topcoat layer c preferably consists of a scratch-resistant varnish (hardcoat, topcoat).
  • This may, for example, be an epoxy varnish, acrylic varnish, including urethane acrylate varnish, polysiloxane varnish, colloidal silica gel varnish or an inorganic/organic hybrid system-based varnish. This is further preferably a polysiloxane varnish, even further preferably produced by the sol-gel process.
  • the topcoat layer c more preferably also contains at least one UV absorber, for example derived from benzophenones, triazoles or triazines.
  • the topcoat layer c preferably has high abrasion and scratch resistance and hence especially fulfills the function of a scratch-resistant coating.
  • the proportion of UV absorber in the topcoat layer is preferably 5% to 15% by weight, further preferably 8% to 12% by weight, based on the total weight of the topcoat layer.
  • topcoat layer c Commercially available systems for the topcoat layer c are, for example, AS4000, SHC5020 and AS4700 from Momentive Performance Materials. Such systems are described for example in U.S. Pat. No. 5,041,313 A, DE 3,121,385 A1, U.S. Pat. No. 5,391,795 A and WO 2008/109072 A1. These materials are typically synthesized via condensation of alkoxy- and/or alkylalkoxysilanes under acid or base catalysis. Nanoparticles can optionally be incorporated. Preferred solvents are alcohols such as butanol, isopropanol, methanol, ethanol and mixtures of these.
  • Various methods for producing a scratch-resistant coating on plastics articles are known. These systems may be applied, for example, by dipping processes, spin-coating, spraying processes or flow coating, preferably by dipping or flow processes. Curing can be effected thermally or by UV irradiation.
  • the scratch-resistant coating may be applied, for example, directly or after preparation of the substrate surface with a primer (primer layer b).
  • the primer layer alternatively or additionally to the topcoat layer, more preferably also contains at least one UV absorber, for example derived from benzophenones, triazoles or triazines.
  • a scratch-resistant coating may also be applied via plasma-assisted polymerization methods, for example via an SiO 2 plasma. Antifogging or antireflection coatings may likewise be produced via plasma methods. It is additionally possible to use certain injection molding processes, for example overmolding of surface-treated films, to apply a scratch-resistant coating on the resulting shaped article.
  • the protective layer as part of the multilayer article comprising at least the topcoat layer may thus be a single- or multilayer system and hence also a combination of two or more layers, etc. More particularly, the protective layer may consist of the layers topcoat layer c and primer layer b, with the primer layer b arranged between topcoat layer c and substrate layer a.
  • the protective layer comprises a
  • derivatives here and hereinafter are understood to mean those compounds having a molecular structure that has, in place of a hydrogen atom or a functional group, a different atom or a different group of atoms or in which one or more atoms/groups of atoms has/have been removed. The parent compound is thus still recognizable.
  • thermoplastic polymer on which the composition used for the substrate layer is based is an aromatic polycarbonate
  • the primer preferably contains further stabilizers, for example HALS systems (stabilizers based on sterically hindered amines), adhesion promoters and/or flow enhancers.
  • HALS systems stabilizers based on sterically hindered amines
  • adhesion promoters adhesion promoters and/or flow enhancers.
  • the respective resin forming the base material of the primer layer b may be selected from a multitude of materials and is described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, vol. A18, pp. 368-426, VCH, Weinheim 1991.
  • polyacrylates polyurethanes, phenol-based systems, melamine-based systems, epoxy systems and alkyd systems, and mixtures of these systems.
  • the resin is usually dissolved in suitable solvents—often in alcohols.
  • suitable solvents often in alcohols.
  • hardening can be effected at room temperature or at elevated temperatures. Preference is given to using temperatures between 50° ° C. and 140° ° C.—often after a large part of the solvent has been removed over a short period at room temperature.
  • examples of commercially available primer systems include SHP470, SHP470-FT2050 and SHP401 from Momentive Performance Materials.
  • Such coatings are described, for example, in U.S. Pat. No. 6,350,512 B1, U.S. Pat. No. 5,869,185 A, EP 1308084 A1 and WO 2006/108520 A1.
  • the polysiloxane layer preferably contains organosilicon compounds having the formula R n SiX 1-n and/or partial condensates thereof,
  • R preferably represents saturated, branched or unbranched alkyl radicals having 1 to 20 carbon atoms and/or represents mono- or polyunsaturated branched or unbranched alkenyl radicals having 2 to 20 carbon atoms or aromatic groups having 6 to 12 carbon atoms.
  • the alkyl/alkenyl radicals further preferably have up to 12, still further preferably up to 8, carbon atoms. More preferably, all radicals are methyl and/or phenyl radicals.
  • X is an alkoxy group, most preferably a C1- to C4-alkoxy group, for example a methoxy group or an ethoxy group.
  • the silicon compounds R n SiX 4-n are hydrolyzable and condensable via the X radicals. These hydrolytically condensable groups are used to construct an inorganic network comprising Si—O—Si units. In contrast to the X radicals, the R radicals are stable to hydrolysis under the typical condensation conditions.
  • dry layer thicknesses of 3 ⁇ m-20 ⁇ m are preferred, further preferably 5 ⁇ m-15 ⁇ m, especially preferably 6 ⁇ m-12 ⁇ m.
  • “Dry layer thickness” means the layer thickness of the topcoat layer c after application, evaporation of the solvent and subsequent thermal or UV curing.
  • the layer thickness may be determined, for example, by white light interferometry (for example by means of a white light interferometer from Eta Optic; ETA-SST), which is preferred.
  • Cross section preparation and microscope detection by optical microscopy or scanning electron microscopy) of the layers may also be used to detect the thickness via material contrast.
  • topcoat layer c In addition, rather than primer/scratch-resistant coating combinations, it is also possible to use one-component hybrid systems as topcoat layer c, either in thermally curable or UV-curable form, for the multilayer articles.
  • Preferred multilayer articles of the invention are those comprising
  • multilayer articles of the invention are those comprising
  • the composition further comprises no further components apart from one or more further additives selected from the group consisting of UV absorbers, demolding agents, thermal stabilizers, antistats, blend partners and flow improvers; most preferably, it comprises at least one UV absorber.
  • Colorants present in the substrate layer are most preferably merely those of the formulae (1) to (18), Amaplast Yellow GHS, the Heliogen Blue grades or the Heliogen Green grades.
  • the thickness of the substrate layer is preferably 0.2 to 10.0 mm, further preferably 0.5 to 8.0 mm, even further preferably 1.0 to 6.0 mm.
  • the topcoat layer is polysiloxane-based with a dry layer thickness of 3 to 20 ⁇ m.
  • the multilayer articles of the invention composed of substrate layer and topcoat layer and optionally further layers, may be produced by (co)extrusion, direct skinning, direct coating, insert molding, in-mold coating, or other suitable methods known to the person skilled in the art.
  • the invention also relates to corresponding products consisting of the multilayer articles of the invention or comprising the multilayer articles of the invention.
  • Such products, shaped bodies or shaped objects that are preferred in accordance with the invention and are composed of or comprise multilayer articles of the invention are, for example, products used in construction applications, especially for outdoor use, such as downpipes and window frames, and also those in automotive applications such as roof modules, outdoor and indoor covers (e.g. bezels), spoilers and mirror housings, and other chassis components and generally vehicle exterior parts, i.e. including exterior parts of, for example, rail vehicles and aircraft.
  • the multilayer articles of the invention may be used for housings or housing elements for outdoor use, for example electrical switchgear boxes, antennas or antenna elements, for instance for 4G or 5G technology, for housings or housing elements of mobile communications base stations, for instance for 4G or 5G technology, pipes etc., for toys and playing equipment for outdoor use, and likewise for lamp covers for the interior of vehicles and buildings, lamp covers for outdoor use, for example covers of streetlights.
  • the compositions of the invention may be used for solid boards, but also for twin-wall sheets or multiwall sheets.
  • Melt volume flow rate was determined according to ISO 1133:2012-03 (at a testing temperature of 300° ° C., mass 1.2 kg) using the Zwick 4106 instrument from Zwick Roell.
  • Transmission measurements (transmission in the VIS region, 380 to 780 nm) were conducted on a Lambda 900 spectrophotometer from Perkin Elmer with a photometer sphere according to ISO 13468-2: 2006 (i.e. determination of total transmission by measurement of diffuse transmission and direct transmission).
  • Color change The samples were measured in reflection according to ASTM E 1331-04. This is used to calculate the color values L*, a*, b* in the CIELAB 1976 color space according to ASTM E 308-08 for the D65 illuminant and the 10° observer.
  • Yellowness index (Y.I.) was determined according to ASTM E 313-15 (observer: 10°/illuminant: D65) on specimen plaques having a sheet thickness of 4 mm.
  • the surface properties were assessed by conducting gloss measurements. For this purpose, the samples were inserted into a gloss measuring instrument and gloss was measured at 60° (ASTM D 2457-08).
  • Visual color impression is determined by the naked eye using color specimen plaques (see production of the test specimens).
  • the color specimen plaques were viewed before a white background in daylight and assessed correspondingly.
  • Kronos 2230 from Kronos Worldwide Inc. This titanium dioxide type features the following characteristics: Titanium dioxide of the rutile type in an amount of more than 93.0% by weight in Kronos 2230; median particle diameter (D50, determined by means of scanning electron microscopy (STEM)) about 0.2 ⁇ m.
  • the outer inorganic layer having a thickness of about 10 nm contains a homogeneous mixture of titanium dioxide and silicon/aluminum oxides (determined by means of x-ray photon electron spectroscopy; XPS). The ratio of silicon+aluminum to titanium, in each case in atom %, is about 1:1.
  • Titanium Dioxide for Inventive Examples:
  • Ti dioxide type features the following characteristics: Titanium dioxide of the rutile type; median particle diameter (D50, determined by means of scanning electron microscopy (STEM)) about 0.7 ⁇ m, determined by means of scanning electron microscopy (STEM).
  • the outer layer having a thickness of about 10 to 15 nm comprises a mixture of titanium dioxide and silicon/aluminum oxides having an elevated proportion of silicon and aluminum oxides (determined by means of x-ray photon electron spectroscopy; XPS).
  • the ratio of the sum total of silicon+aluminum to titanium, in each case in atom %, in the coating is about 20:1. This ratio is also found at a detection angle of 45°.
  • Ti dioxide type features the following characteristics: Titanium dioxide of the rutile type; median particle diameter (D50, determined by means of scanning electron microscopy (STEM)) about 1.1 ⁇ m, determined by means of scanning electron microscopy (STEM).
  • the outer layer having a thickness of about 10-15 nm comprises a mixture of titanium dioxide and silicon/aluminum oxides having an elevated proportion of silicon and aluminum oxides (determined by means of x-ray photon electron spectroscopy; XPS).
  • the ratio of the sum total of silicon+aluminum to titanium, in each case in atom %, in the coating is about 20:1. This ratio is also found at a detection angle of 45°.
  • Composition consisting of polycarbonate from Covestro GmbH AG with an MVR of about 12 cm 3 /(10 min), measured at 300° C. with a load of 1.2 kg (to ISO 1133-1:2012-03), based on bisphenol A and terminated by phenol, and 0.20% by weight of Tinuvin 329 (UV absorber) and 0.30% by weight of pentaerythritol tetrastearate (demolding agent).
  • Polycarbonate from Covestro Deutschland AG having an MVR of about 12 cm 3 /(10 min), measured at 300° C. and load 1.2 kg (to ISO 1133-1:2012-03) and based on bisphenol A and terminated by phenol.
  • the polycarbonate does not contain any further additives.
  • Polycarbonate from Covestro Deutschland AG having an MVR of about 6 cm 3 /(10 min), measured at 300° C. and load 1.2 kg (to ISO 1133-1:2012-03) and based on bisphenol A and terminated by phenol.
  • the polycarbonate does not contain any further additives.
  • Polycarbonate from Covestro GmbH AG having an MVR of about 12 cm 3 /(10 min), measured at 300° C. and load 1.2 kg (to ISO 1133-1:2012-03) and based on bisphenol A and terminated by phenol, containing 0.30% by weight of pentaerythritol tetrastearate (demolding agent).
  • Heat-stable, micronized iron oxide red pigment having CAS number 001309-37-1 from Lanxess GmbH.
  • Carbon black for the coloring of plastics from Cabot Corp.
  • Carbon black for the coloring of plastics from The Cary Company 1195 W. Fullerton Ave, Addison IL 60101.
  • Macrolex Red EG Macrolex Red EG
  • Solvent Yellow 114 Disperse Yellow 54 quinophthalone dye from Lanxess Germany GmbH.
  • Oracet Yellow 180 (Oracet Yellow GHS):
  • Anthraquinone dye Solvent Yellow 163 from BASF SE, Ludwigshafen, Germany.
  • Paliogen Blue L 6385 (Pigment Blue 60) with CAS number 81-77-6 from BASF SE, 67065 Ludwigshafen, Germany. This colorant has a bulk volume of 7 l/kg, a pH of 6-9 and a specific surface area of 40 m 2 /g.
  • Ni/Sb/Ti oxide with CAS number 8007-18-9 from BASF SE, Ludwigshafen, Germany.
  • Pigment Blue 29 with CAS number 057455-37-5 from Nubiola Fero Corp.; Mayfield Heights, Ohio, USA.
  • TPP Triphenylphosphine
  • Richfos 168 (80% by weight) and Richox 1076 (20% by weight), Richfos 168 being tris(2,4-di-tert-butylphenyl) phosphite with CAS number 31570-04-4 and Richnox 1076 being octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; Rich Yu Chemical B.V., The Netherlands.
  • Tinuvin® 329 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole with CAS number 3147-75-9 from BASF SE, Ludwigshafen, Germany.
  • Triisooctyl phosphate (TOF; tris-2-ethylhexyl phosphate) with CAS number 78-42-2. Disflamoll TOF from Lanxess Germany GmbH.
  • the additives were compounded with the amounts of components specified in the examples on a KraussMaffei Berstorff ZE25 twin-screw extruder at a barrel temperature of 260° C. or a melt temperature of 270° C. and at a speed of 100 rpm at a throughput of 10 kg/h.
  • a powder mixture (10% by weight of powder mixture, based on the overall composition) containing the additives was made up here. This powder mixture was metered into the remaining polycarbonate in the course of compounding.
  • the pelletized material was dried at 120° C. under reduced pressure for 3 hours and then processed on an Arburg 370 injection molding machine with a 25 injection unit at a melting temperature of 300° ° C. and a mold temperature of 90° ° C. to give color specimen plaques of dimensions 60 mm ⁇ 40 mm x Z mm, where Z is 3.2 mm, 4.0 mm or 5.0 mm.
  • the primer used was the product SHP470FT (Momentive Performance Materials Inc. Wilton, CT USA).
  • the protective varnish used was the product AS 4700 (Momentive Performance Materials Inc. Wilton, CT USA).
  • Coating was effected in a coating chamber with a controlled atmosphere under the respective stipulations of the coating manufacturer, at 23 to 25° C. and at 40% to 48% relative humidity.
  • test specimens were cleaned using so-called iso wipes (LymSat® from LymTech Scientific; saturated with 70% isopropanol and 30% deionized water), rinsed off with isopropanol, dried in air for 30 minutes and blown with ionized air.
  • iso wipes LiSat® from LymTech Scientific; saturated with 70% isopropanol and 30% deionized water
  • test specimens were coated by hand by the flow-coating method. This involved pouring the primer solution over the sheet in the longitudinal direction starting from the upper edge of the small part, while the starting point of the primer on the sheet was simultaneously guided from left to right across the width of the sheet.
  • the primed sheet was ventilated until dust-dry hanging vertically on a clip and cured in an air circulation oven according to the respective manufacturer's stipulations (ventilated at room temperature for 30 minutes and cured at 125° ° C. for 30 minutes). Cooling to room temperature was followed by coating of the primed surface with AS 4700. Ventilation until dust-dry was followed by curing at 130° ° C. in an air circulation oven for 60 min.
  • the primer layer thickness and the thickness of the topcoat can affect the weathering properties.
  • the primer layer thickness for the examples that follow was in the range of 1.2-4.0 ⁇ m, and the thickness of the topcoat between 4.0 and 8.0 ⁇ m.
  • compositions for a green, red, yellow and brown color setup are detailed in comparative examples 3-1 to 3-4. As in comparative examples 2-1 to 2-5, the compositions are unstable to weathering.
  • titanium dioxide-containing pigments interact with UV radiation and hence have high photoactivity.
  • a relatively high UV absorber content in the substrate layer has, surprisingly, no influence on weathering stability in the case of Kronos 2230 titanium dioxide pigment optimized for polycarbonate.
  • compositions containing no titanium dioxide are very stable to weathering. However, such hues have a dull color impression of low brilliance. Since titanium dioxide breaks down organic colorants as a result of the photoactivity discussed, the person skilled in the art would have expected an increase in the color concentration of organic colorants in the compositions to contribute to elevated stability. However, this is surprisingly not the case (C. 6-1, C. 6-2).
  • compositions have light transmittance of ⁇ 0.5% in the range from 380 to 780 nm, determined at a sheet thickness of 4 mm to DIN ISO 13468-2:2006 (D65, 10°).
  • compositions 7-1 to 7-4 together with a UV paint system as coating completely surprisingly result in a weathering-stable multilayer article.
  • the combination of titanium dioxide for use in accordance with the invention having a specific minimum particle size and coating composition comprising Kronos 2230 does not lead to weathering-stable multilayer articles. This could not be assumed from the small or zero differences in the case of uncoated test specimens.
  • the titanium dioxide for use in accordance with the invention with the greatest particle size (D50) gives the most stable compositions for the multilayer articles of the invention.
  • UV absorbers in combination with the titanium dioxide grades to be used in accordance with the invention display a positive effect. This was likewise not to be expected in the light of the comparative examples with elevated UV absorber content.
  • compositions 8-1 to 8-3 Compositions 8-1 to 8-3. Ex. 8-1 Ex. 8-2 Ex. 8-3 Starting material % by weight % by weight % by weight PC2 95.0 95.0 95.0 PC3 4.5 4.5 4.5 4.5 Altiris 550 0.5 Altiris 800 0.5 Kronos 2230 0.5
  • compositions containing a non-polycarbonate-optimized titanium dioxide pigment do not show significantly lower melt stability than compositions containing a polycarbonate-optimized titanium dioxide grade (Kronos 2230, ex. 8-3).

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CN117849156B (zh) * 2023-12-28 2024-09-13 国家地质实验测试中心 一种低Re含量碳酸盐岩Re-Os同位素定年方法

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EP3802121B1 (de) 2022-07-20
EP3802121A1 (de) 2021-04-14
US20210221977A1 (en) 2021-07-22
CN112334306A (zh) 2021-02-05
KR20210016563A (ko) 2021-02-16
KR102822128B1 (ko) 2025-06-19
CN112334306B (zh) 2023-04-07
JP2021531995A (ja) 2021-11-25
WO2019228959A1 (de) 2019-12-05

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